CN103273614A - Method for toughening isotatic polypropylene iPP product by using atactic polypropylene as elastomer - Google Patents
Method for toughening isotatic polypropylene iPP product by using atactic polypropylene as elastomer Download PDFInfo
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- CN103273614A CN103273614A CN2013101938310A CN201310193831A CN103273614A CN 103273614 A CN103273614 A CN 103273614A CN 2013101938310 A CN2013101938310 A CN 2013101938310A CN 201310193831 A CN201310193831 A CN 201310193831A CN 103273614 A CN103273614 A CN 103273614A
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Abstract
The invention discloses a method for toughening isotatic polypropylene iPP product by using atactic polypropylene as an elastomer. The method comprises the following steps of: preparing an aPP (atactic polypropylene)/iPP blend, namely, carrying out melt blending and extruding on aPP and iPP aggregates in a twin-screw extruder, wherein the content of the aPP in the blend is lower than 30wt%; and drying and carrying out injection moulding to manufacture the aPP/iPP blend aggregates into the product on a common injection molding machine. According to the method disclosed by the invention, the internal structure of the product is improved by changing the technical parameters in processing so as to improve the mechanical performance, and the shish-kebab structure formed by a flow field in the injection molding process is applied while the aPP is used to toughen the iPP, so that the product has more perfect comprehensive performance, therefore, not only is the toughness of the isotatic polypropylene product improved, but also the aPP byproduct is adequately utilized. The production cost is lowered.
Description
Technical field
The invention belongs to processing of high molecular material and polymer blended field of material preparation, relate generally to the preparation of random polypropylene (aPP)/isotactic polypropylene (iPP) intermingling material injection-molded item, and the efficient utilization of random polypropylene (aPP).
Background technology
Polypropylene (PP) is as a kind of commodity polymer material, because its excellent comprehensive performance has obtained using widely in all fields.Distribution by methyl on its side chain can be divided into isotactic polypropylene (iPP), random polypropylene (aPP) and syndiotactic polypropylene (sPP).IPP the most commonly wherein is with its excellent comprehensive performance, as easily processing, high-fire resistance and high strength etc., in injection moulding, extrude, be widely used in the production such as blowing.Yet, iPP goods in conventional processing method acquisition, its crystal (being generally spherocrystal) size is big, it is few that intergranular connects molecule, the toughness of goods is lower, especially low-temperature flexibility is poorer, and this has greatly limited the expansion of iPP application, thereby the iPP goods are carried out the toughness reinforcing extensive concern that has been subjected to academia and industrial quarters.At present, the toughness of improving the iPP goods has four kinds of methods commonly used, i.e. copolymerization [P.Galli, et al.Prog.Polym.Sci.2001,26,1287.], with thermoplastic elastic body blend [C.Bucknall, et al.Macromol.Symp.1996,101,265.], utilize inorganic particulate or the toughness reinforcing [R.Karnani of Nano filling, et al.Polym.Eng.Sci.1997,37,476.] and add beta nucleater [J.Varga.J.Macromol.Sci., Phys.2002,41,1121].Wherein, adopt copolymerization or to add elastomeric mode cost higher; Add the method for inorganic particulate also because the interface compatibility of inorganic particulate and iPP is relatively poor, so can significantly reduce intensity toughness reinforcing the time; Though adding beta nucleater is a kind of effective toughness reinforcing mode, and production technology is had higher requirement.
APP is a kind of accessory substance in the iPP building-up process, because the efficient of catalyst can not reach 100%, so aPP always produces inevitably.Though at present industrial for the synthetic catalyst efficiency of PP substantially all more than 95%, in view of the annual huge output of PP, the absolute yield of aPP is still considerable.APP is not owing to possess stereoregularity, thereby uncrystallizable, its glass transition temperature (T
g) about 0 ℃.Under the normal temperature, according to the difference of molecular weight, aPP shows as the oily liquids of thickness or the elastomer that the wax shape is clamminess.Generally, the aPP molecular weight is low, molecular weight distribution is wideer, structure irregularity, cohesive force are low, thereby mechanical performance and hear resistance relatively poor [J.Yang, et al.J.Appl.Polym.Sci.2005,98,1087.].At present, aPP is mainly used in modified asphalt waterproof coiled material, preparation filling master batch and as low value-added applications such as PURs.In petroleum resources today in short supply day by day, this is undoubtedly a kind of great waste.How with efficient, the high annex value of aPP use and just become a problem demanding prompt solution.
Consider that aPP is a kind of elastomer, and have similar molecular structure and good compatibility to iPP, thereby it is added to carry out toughness reinforcing among the iPP be a kind of selection that makes exploration.This method possesses following advantage: at first, aPP is as a kind of production accessory substance, and is relatively cheap, thereby cost is lower; Secondly, have and report that aPP and iPP have good compatibility [R.Maier, et al.J.Polym.Sci.Part B:Polym.Phys.1997,35,1135.] under melt state, thereby both mix easily, do not need special process equipment; The difference of the 3rd, aPP and iPP only is the arrangement of methyl in the strand, and both good compatibilities also make the addition of aPP arbitrarily control, and do not have the problem of interface compatibility difference; The 4th, this method can efficiently, high added value be utilized aPP in a large number, thereby saves precious petroleum resources.
But the toughness reinforcing iPP of aPP faces a bottleneck problem, and the affiliation that adds that is exactly aPP causes the iPP mechanical strength significantly to reduce.Its reason is that the general molecular weight of aPP is low, and the molecular structure irregularity is uncrystallizable, lacks the crosslinking points of physics or chemistry, is difficult to after the deformation reply, so mechanical property is very poor, therefore aPP is joined the deterioration that can cause mechanical property among the iPP inevitably.Studies show that field of flow is induced the oriented crystal (being shish-kebab, the shish-kebab structure) of formation, can give mechanical property, wear resistance and the anti-fatigue performance [B.Schrauwen, et al.Macromolecules2004,37,8618.] of material excellence.Therefore we expect to form the shish-kebab structure in the injection-molded item of aPP/iPP blend, remedy because of aPP to add the mechanical property deterioration that causes.
Also few about the patent of random polypropylene at present.Relevant patent mainly concentrates on synthetic used catalyst and random polypropylene and the isotactic polypropylene copolymer of random polypropylene.For example: for the preparation of the catalyst (patent No. 001142380) of intermediate molecular weight random polypropylene; The preparation method of atactic polypropylene catalyst (patent No. 991003594); Atactic polypropylene catalyst (patent No. 941012751); The method (patent No. 031396941) for preparing random polypropylene elastomer and ethylene/propene copolymer; Preparation (patent No. 2006800391704) based on polymer and the block copolymer of isotactic polypropylene and regional random polypropylene.Do not retrieve the relevant patent of random polypropylene/isotactic polypropylene blend preparation, do not retrieve yet and use random polypropylene that isotactic polypropylene is carried out toughness reinforcing relevant patent documentation.
Summary of the invention
Above shortcoming in view of prior art the purpose of this invention is to provide the process conditions of groping the toughness reinforcing iPP goods of aPP, improves the toughness of iPP goods under the basic condition that keeps other intensity index, and provides a path for the aPP material that utilizes of high added value.
The objective of the invention is to realize by following means:
A kind of with the method for random polypropylene as elastic body toughening isotactic polypropylene iPP goods, comprise following processing step:
(1) aPP/iPP blend preparation: melt blending in double screw extruder is extruded with random polypropylene aPP and isotactic polypropylene iPP pellet, and the content of random polypropylene is lower than 30wt% in the blend; Each section of extruder barrel temperature is 120～210 ℃, and the material bar of extruding carries out pelletizing after immersing the cold water cooling, obtains uniform aPP/iPP blend pellet;
(2) drying: the aPP/iPP blend that step (1) is made places air dry oven to carry out drying, and baking temperature is 50～80 ℃, until aggregate moisture content less than 0.01%;
(3) injection mo(u)lding: dried aPP/iPP blend pellet in the step (2) is processed as goods at common injection machine, the barrel temperature of injection machine is 120～200 ℃, 190～200 ℃ of nozzle temperatures, mold temperature is 40～80 ℃, the injection moulding dwell time is greater than 1min, and adopts big valve gated mold.
The present invention improves the internal structure of goods to improve its mechanical property by the technological parameter that changes in the processing, utilize the iPP of aPP carry out toughness reinforcing in, the shish-kebab structure of using the field of flow in the injection moulding process to form, adopt big valve gated mold and long dwell time to improve degree of crystallinity and the compaction rate of goods, make article construction more perfect, thereby improve its combination property.Have following tangible advantage:
At first, aPP and iPP can complete miscibilities at melt state, and the fusing point of aPP own is also lower, easily processing, therefore the preparation of aPP/iPP blend is handled without any need for special mixing facilities and early stage, directly extrudes through common twin-screw to reach requirement.Both similar molecular structures have also been given blend good interface compatibility, and two kinds of raw materials all do not need processing such as modification or grafting.
Secondly, adopt rational processing method under the situation that does not add other reinforcers, to improve the mechanical property of goods in the inner shish-kebab structure that forms self-reinforcing of goods, be convenient to the recycling of waste product.
The 3rd, by the regulation and control processing method, namely generate the shish-kebab structure of self-reinforcing by the field of flow of injection moulding process, adopt big valve gated mold and long dwell time to improve degree of crystallinity and the compaction rate of goods, utilize the toughness reinforcing iPP goods of the aPP purpose of little amplitude reduction product strength again thereby reach, for extensive, high value added utilization aPP have opened a new passage.
Description of drawings is as follows:
Fig. 1 is the stress-strain diagram of each embodiment and comparative example;
Fig. 2 is observed shish-kebab structure in embodiment 1 goods;
Fig. 3 is observed shish-kebab structure in embodiment 2 goods.
The prescription of Fig. 4 embodiment 1-3 and comparative example 1.
Fig. 5 is hot strength and the toughness of each embodiment and comparative example;
The degree of crystallinity of Fig. 6 embodiment 1-3 and comparative example 1 goods.
The specific embodiment
Embodiment given below is, and the present invention specifically describes.Be necessary to be pointed out that at this following examples are only for the present invention is further illustrated; can not be interpreted as limiting the scope of the invention, this art skilled person still belongs to protection scope of the present invention according to the invention described above content to nonessential improvement and the adjustment that the present invention makes.The melt flow rate (MFR) (MFR) of the isotactic polypropylene raw material in following examples is 2g/10min, and by the Dushanzi petrochemical iy produced, its trade mark is S1003.The aPP that adopts is the secondary board product of Exxon Mobil Corporation, is slightly yellowish particle.
1. prepare the aPP/iPP intermingling material: place the double screw extruder melt blending to extrude the aPP/iPP blend (concrete prescription is seen Fig. 4) of different content, obtain uniform aPP/iPP blend.Each section of extruder barrel temperature is respectively: 120,160,190,210 ℃, the extrusion neck ring mold temperature is 200 ℃, and screw speed is 150rpm, and the material bar of extruding immerses after drawing forces cooling in the cold water that temperature is lower than 25 ℃, and granulation is standby afterwards.
2. dry: the aPP/iPP blend pellet that extruding pelletization is made places air dry oven to carry out drying, and baking temperature is 80 ℃, and be 4h drying time, and thickness of feed layer is not more than 2cm.
3. injection mo(u)lding: then that drying is good pellet carries out injection mo(u)lding, each section of screw in injection molding machine temperature is: 120,180,190,200 ℃, nozzle place temperature is 200 ℃, injection pressure is 8MPa, dwell pressure is 5MPa, mold temperature adopts 80 ℃, and the dwell time is 3min, adopts the circular cast gate of 8mm.
1. prepare the aPP/iPP intermingling material: place the double screw extruder melt blending to extrude the aPP/iPP blend (concrete prescription is seen Fig. 4) of different content, obtain uniform aPP/iPP blend.Each section of extruder barrel temperature is respectively: 120,160,190,210 ℃, the extrusion neck ring mold temperature is 200 ℃, and screw speed is 150rpm, and the material bar of extruding immerses after drawing forces cooling in the cold water that temperature is lower than 25 ℃, and granulation is standby afterwards.
2. dry: the aPP/iPP blend pellet that extruding pelletization is made places air dry oven to carry out drying, and baking temperature is 60 ℃, and be 5h drying time, and thickness of feed layer is not more than 2cm.
3. injection mo(u)lding: then that drying is good pellet carries out injection mo(u)lding, and each section of screw in injection molding machine temperature is: 120,180,190,200 ℃, nozzle place temperature is 190 ℃, injection pressure is 8MPa, dwell pressure is 5MPa, and mold temperature adopts 60 ℃, and the dwell time is 3min.Adopt the circular cast gate of 8mm.
1. prepare the aPP/iPP intermingling material: the aPP/iPP blend of different content (is specifically filled a prescription and seen that Fig. 4 places the double screw extruder melt blending to extrude, and obtains uniform aPP/iPP blend.Each section of extruder barrel temperature is respectively: 120,160,190,210 ℃, the extrusion neck ring mold temperature is 200 ℃, and screw speed is 150rpm, and the material bar of extruding immerses after drawing forces cooling in the cold water that temperature is lower than 25 ℃, and granulation is standby afterwards.
2. dry: the aPP/iPP blend pellet that extruding pelletization is made places air dry oven to carry out drying, and baking temperature is 50 ℃, and be 6h drying time, and thickness of feed layer is not more than 2cm.
3. injection mo(u)lding: then that drying is good pellet carries out injection mo(u)lding, and each section of screw in injection molding machine temperature is: 120,180,190,200 ℃, nozzle place temperature is 190 ℃, injection pressure is 8MPa, dwell pressure is 5MPa, and mold temperature adopts 40 ℃, and the dwell time is 3min.
Comparative example 1
Press the ratio of component of comparative example 1 among Fig. 4, with material injection moulding, the control technological parameter is identical with embodiment, prepares pure iPP goods to make performance relatively.
Mechanical property
For estimating feasibility of the present invention, it is the toughening effect of the iPP goods of aPP, and aPP adds the variation of back product strength, the Mechanics Performance Testing of each embodiment and comparative example is according to carrying out under the guidance of ASTMD-638 standard, rate of extension is 50mm/min, probe temperature is room temperature (23 ℃), and experimental result as depicted in figs. 1 and 2.
As seen from Figure 1, along with the adding of aPP, the goods load-deformation curve changes ductile rupture into by brittle fracture, though hot strength decreases, elongation at break increases greatly, and this toughness that shows goods increases to some extent than comparative example.Further analyze area (being defined as toughness) and hot strength under each embodiment and the comparative example load-deformation curve, as shown in Figure 5, as seen, the hot strength of embodiment 1 (aPP content is 10wt%) and embodiment 2 (aPP content is 20wt%) is 40.49MPa, (pure iPP) only descended about 5MPa with respect to comparative example, but toughness all increases to some extent.For comparative example 3 (aPP content is 30wt%), hot strength declines to a great extent to 28.20MPa, but toughness is only by the 42.62MJ/m of embodiment 2
3Increase to 45.31MJ/m
3, visible continuation increase aPP content toughness improves limited but intensity declines to a great extent.
By top result as can be seen, the aPP that is lower than 30wt% by interpolation can increase substantially the toughness of iPP goods, and hot strength has obtained sufficient maintenance when aPP content is low simultaneously.
Morphologic observation
In order to explore the reason that comparative example 1 and comparative example 2 mechanical properties are fully kept, to utilize SEM (SEM) that goods are quenched and observe behind section etching, the metal spraying, unit type is the Inspect-F that FEI Co. produces, accelerating potential is 20kV.The SEM image that obtains as shown in Figures 2 and 3.As can be seen, in injection moulding process under the effect of field of flow, a large amount of shish-kebab structures has all appearred in the cortex of embodiment 1 and embodiment 2 goods, these height-oriented crystal structures have played important function for the raising of goods mechanical property, have remedied to a certain extent because aPP adds the mechanical property deterioration that causes.
Degree of crystallinity
As everyone knows, the raising of degree of crystallinity plays an important role for the improvement of goods mechanical property, in order to probe into iPP component crystallinity change situation in each embodiment and the comparative example, each example has been carried out the DSC test, the DSC Q-2000 that experimental facilities is produced for TA company, heating rate in the experimentation is 10 ℃/min, and experimental result as shown in Figure 6.As seen from Figure 6, compared to comparative example, the degree of crystallinity of iPP component all is improved to some extent among all embodiment.Explanation thus, big valve gated mold and long dwell time are conducive to the perfect of goods internal crystallization structure, have improved the degree of crystallinity of goods to a certain extent, are conducive to maintenance and the raising of goods mechanical property.
Claims (3)
1. one kind with the method for random polypropylene as elastic body toughening isotactic polypropylene iPP goods, comprises following processing step:
(1) aPP/iPP blend preparation: melt blending in double screw extruder is extruded with random polypropylene aPP and isotactic polypropylene iPP pellet, and the content of random polypropylene is lower than 30wt% in the blend; Each section of extruder barrel temperature is 120～210 ℃, and the material bar of extruding carries out pelletizing after immersing the cold water cooling, obtains uniform aPP/iPP blend pellet;
(2) drying: the aPP/iPP blend that step (1) is made places air dry oven to carry out drying, and baking temperature is 50～80 ℃, until aggregate moisture content less than 0.01%;
(3) injection mo(u)lding: dried aPP/iPP blend pellet in the step (2) is processed as goods at common injection machine, the barrel temperature of injection machine is 120～200 ℃, 190～200 ℃ of nozzle temperatures, mold temperature are 40～80 ℃, injection volume during less than 500g the dwell time greater than 1min; And adopt big valve gated mold.
According to claim 1 described with the method for random polypropylene as elastic body toughening isotactic polypropylene iPP goods, it is characterized in that the content of random polypropylene is 20wt% in the described blend.
According to claim 1 described with the method for random polypropylene as elastic body toughening isotactic polypropylene iPP goods, it is characterized in that the described injection moulding dwell time is 3min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113427732A (en) * | 2021-06-29 | 2021-09-24 | 四川大学 | Method for inducing formation of Shish-kebab precursor in polypropylene random copolymer by using waste IPP (interpenetrating polymer network) material |
Citations (4)
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|---|---|---|---|---|
| JPS5889635A (en) * | 1981-11-25 | 1983-05-28 | Hitachi Ltd | Polypropylene resin composition |
| US5539056A (en) * | 1995-01-31 | 1996-07-23 | Exxon Chemical Patents Inc. | Thermoplastic elastomers |
| US5686533A (en) * | 1995-10-16 | 1997-11-11 | Pcd Polymere Gesellschaft M.B.H. | Polypropylenes having a reduced tendency to white fracture |
| CN1408011A (en) * | 1999-12-10 | 2003-04-02 | 埃克森化学专利公司 | Method of preparation of crosslinked blends of amorphous and crystalline polymers |
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2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5889635A (en) * | 1981-11-25 | 1983-05-28 | Hitachi Ltd | Polypropylene resin composition |
| US5539056A (en) * | 1995-01-31 | 1996-07-23 | Exxon Chemical Patents Inc. | Thermoplastic elastomers |
| US5686533A (en) * | 1995-10-16 | 1997-11-11 | Pcd Polymere Gesellschaft M.B.H. | Polypropylenes having a reduced tendency to white fracture |
| CN1408011A (en) * | 1999-12-10 | 2003-04-02 | 埃克森化学专利公司 | Method of preparation of crosslinked blends of amorphous and crystalline polymers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113427732A (en) * | 2021-06-29 | 2021-09-24 | 四川大学 | Method for inducing formation of Shish-kebab precursor in polypropylene random copolymer by using waste IPP (interpenetrating polymer network) material |
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